CA2080459C - Compositions for moisture curing hot melt adhesives - Google Patents
Compositions for moisture curing hot melt adhesives Download PDFInfo
- Publication number
- CA2080459C CA2080459C CA002080459A CA2080459A CA2080459C CA 2080459 C CA2080459 C CA 2080459C CA 002080459 A CA002080459 A CA 002080459A CA 2080459 A CA2080459 A CA 2080459A CA 2080459 C CA2080459 C CA 2080459C
- Authority
- CA
- Canada
- Prior art keywords
- weight
- parts
- hot melt
- moisture curing
- melt adhesives
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 238000013008 moisture curing Methods 0.000 title claims abstract description 80
- 239000000203 mixture Substances 0.000 title claims abstract description 68
- 239000004831 Hot glue Substances 0.000 title claims abstract description 66
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 150000001875 compounds Chemical group 0.000 claims abstract description 22
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 229920005989 resin Polymers 0.000 claims description 35
- 239000011347 resin Substances 0.000 claims description 35
- 229920005862 polyol Polymers 0.000 claims description 31
- 150000003077 polyols Chemical class 0.000 claims description 25
- 229920001169 thermoplastic Polymers 0.000 claims description 18
- -1 polyol hydride Chemical class 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 13
- 229920002554 vinyl polymer Polymers 0.000 claims description 13
- 229920001281 polyalkylene Polymers 0.000 claims description 7
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 6
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 6
- 229920001400 block copolymer Polymers 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 239000005062 Polybutadiene Substances 0.000 claims description 5
- 229920002857 polybutadiene Polymers 0.000 claims description 5
- 229920005906 polyester polyol Polymers 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 239000005056 polyisocyanate Chemical group 0.000 claims description 3
- 229920001228 polyisocyanate Chemical group 0.000 claims description 3
- 239000005060 rubber Substances 0.000 claims description 3
- 150000003505 terpenes Chemical class 0.000 claims description 3
- 235000007586 terpenes Nutrition 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920001038 ethylene copolymer Polymers 0.000 claims 1
- 230000009257 reactivity Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 26
- 230000001070 adhesive effect Effects 0.000 description 25
- 239000000853 adhesive Substances 0.000 description 20
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 14
- 150000001412 amines Chemical class 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000007983 Tris buffer Substances 0.000 description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 238000001723 curing Methods 0.000 description 5
- 239000013032 Hydrocarbon resin Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 229920006270 hydrocarbon resin Polymers 0.000 description 4
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- MSFGZHUJTJBYFA-UHFFFAOYSA-M sodium dichloroisocyanurate Chemical compound [Na+].ClN1C(=O)[N-]C(=O)N(Cl)C1=O MSFGZHUJTJBYFA-UHFFFAOYSA-M 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- QLZJUIZVJLSNDD-UHFFFAOYSA-N 2-(2-methylidenebutanoyloxy)ethyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OCCOC(=O)C(=C)CC QLZJUIZVJLSNDD-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000004839 Moisture curing adhesive Substances 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- MDRWOAQZCGCEQK-UHFFFAOYSA-N cyclohexane;1,2-diisocyanatobenzene Chemical compound C1CCCCC1.O=C=NC1=CC=CC=C1N=C=O MDRWOAQZCGCEQK-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000012970 tertiary amine catalyst Substances 0.000 description 1
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2081—Heterocyclic amines; Salts thereof containing at least two non-condensed heterocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
- C08G18/2018—Heterocyclic amines; Salts thereof containing one heterocyclic ring having one nitrogen atom in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
- C08G2170/20—Compositions for hot melt adhesives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention provides a composition for moisture curing hot melt adhesives which is superior in both moisture curing reactivity after adhesion and thermal stability during use. The composition of said moisture curing hot melt adhesives is characterized by containing a urethane prepolymer having one or more terminal isocyanate groups and a compound having the structure represented by the following formula (I):
(see formula I) (where X, Y and Z in the formula (I) are alkyl groups or groups represented by the following formula (II), and at least one of X, Y and Z is a group represented by the formula (II):
(see formula II) n in the formula (II) is an integer from 1 through 10, and R1 and R2 are hydrogen or alkyl groups.)
(see formula I) (where X, Y and Z in the formula (I) are alkyl groups or groups represented by the following formula (II), and at least one of X, Y and Z is a group represented by the formula (II):
(see formula II) n in the formula (II) is an integer from 1 through 10, and R1 and R2 are hydrogen or alkyl groups.)
Description
The present invention relates generally to compositions for moisture curing hot melt adhesives using a urethane prepolymer. Said compositions for moisture curing hot melt adhesives exhibit superior thermal stability and superior initial adhesive strength.
Moisture curing hot melt adhesives composed of a urethane prepolymer having an isocyanate group in its end have been conventionally known. For example, Japanese Patent Laid-Open Gazette No. 189486/1988 and Japanese Patent Laid-Open Gazette No. 284577/1989 disclose moisture curing hot melt adhesives using a urethane prepolymer which are superior in intial adhesive strength.
Furthermore, an organic metal compound such as dibutyl tin dilaurate or tin octate or a tertiary amine compound such as triethylamine or triethylenediamine has been added as a catalyst to known types of moisture curing hot melt adhesives.
The initial heat resistance of the above described moisture curing adhesives composed of the urethane prepolymer depends on the softening point, similar to the case of ordinary hot melt adhesives. Thus, an extensive time: period is required before the adhesives exhibit practical heat resistance with polymerization proceeding via moisture curing.
Consequently, an adherend must be subjected to aging for two to three days after adhesion. As a result, in the conventional adhesives disclosed in the above described prior art, the adherend must be aged for extensive time periods, so that the productivity of a bonding operation cannot be sufficiently increased. This is uneconomical.
If the above described catalyst composed of either an organic metal compound or a tertiary amine compound is added, the moisture curing characteristics of the adhesives can be enhanced, thereby allowing a shorter curing time period. However, if the catalyst composed of an organic metal compound or a tertiary amine compound is added, the thermal stability of the adhesives is significantly lowered, so that the adhesives may, in some cases, be gelled in a coating machine.
More specifically, for' conventional moisture curing hot melt adhesives composed of urethane prepolymer, both the curing speed aind the thermal stability cannot be made adequate. Thus, improvements have been required.
The present invention has been made to satisfy the above described requirements and accordingly provides compositions for moisture curing hot melt adhesives superior in reactivity with moisture, exhibiting sufficient thermal resistance within a short time after adhesion, and superior in thermal stability during use.
As a result of zealously examining moisture curing hot melt adhesives using a urethane prepolymer which satisfy the above described requirements, the inventors have found that these requirements can be satisfied if compounds having a particular structure are used as catalysts.
In accordance with a broad aspect of the present invention, there is provided a composition for moisture curing hot melt adhesives which is characterized by containing a urethane prepolymer having an isocyanate group in its end and a compound having a structure represented by the following formul<~ (I):
X _- _ N Z ... ( ... I
) Y
In the formula (I), X, Y and Z are alkyl groups or groups represented by the following formula (II), and at least one of X, Y and Z i:; a group represented by the following formula (II):
Ri --~- C H 2 ~-n N Q ... ... ( I I ) In the formula (II), n is an integer 'from 1 through 10, and R, and R2 are alkyl groups or hydrogen.
Moisture curing hot melt adhesives composed of a urethane prepolymer having an isocyanate group in its end have been conventionally known. For example, Japanese Patent Laid-Open Gazette No. 189486/1988 and Japanese Patent Laid-Open Gazette No. 284577/1989 disclose moisture curing hot melt adhesives using a urethane prepolymer which are superior in intial adhesive strength.
Furthermore, an organic metal compound such as dibutyl tin dilaurate or tin octate or a tertiary amine compound such as triethylamine or triethylenediamine has been added as a catalyst to known types of moisture curing hot melt adhesives.
The initial heat resistance of the above described moisture curing adhesives composed of the urethane prepolymer depends on the softening point, similar to the case of ordinary hot melt adhesives. Thus, an extensive time: period is required before the adhesives exhibit practical heat resistance with polymerization proceeding via moisture curing.
Consequently, an adherend must be subjected to aging for two to three days after adhesion. As a result, in the conventional adhesives disclosed in the above described prior art, the adherend must be aged for extensive time periods, so that the productivity of a bonding operation cannot be sufficiently increased. This is uneconomical.
If the above described catalyst composed of either an organic metal compound or a tertiary amine compound is added, the moisture curing characteristics of the adhesives can be enhanced, thereby allowing a shorter curing time period. However, if the catalyst composed of an organic metal compound or a tertiary amine compound is added, the thermal stability of the adhesives is significantly lowered, so that the adhesives may, in some cases, be gelled in a coating machine.
More specifically, for' conventional moisture curing hot melt adhesives composed of urethane prepolymer, both the curing speed aind the thermal stability cannot be made adequate. Thus, improvements have been required.
The present invention has been made to satisfy the above described requirements and accordingly provides compositions for moisture curing hot melt adhesives superior in reactivity with moisture, exhibiting sufficient thermal resistance within a short time after adhesion, and superior in thermal stability during use.
As a result of zealously examining moisture curing hot melt adhesives using a urethane prepolymer which satisfy the above described requirements, the inventors have found that these requirements can be satisfied if compounds having a particular structure are used as catalysts.
In accordance with a broad aspect of the present invention, there is provided a composition for moisture curing hot melt adhesives which is characterized by containing a urethane prepolymer having an isocyanate group in its end and a compound having a structure represented by the following formul<~ (I):
X _- _ N Z ... ( ... I
) Y
In the formula (I), X, Y and Z are alkyl groups or groups represented by the following formula (II), and at least one of X, Y and Z i:; a group represented by the following formula (II):
Ri --~- C H 2 ~-n N Q ... ... ( I I ) In the formula (II), n is an integer 'from 1 through 10, and R, and R2 are alkyl groups or hydrogen.
Furthermore, in accordance with another broad aspect of the present invention, there is provided a composition for moisture curing hot melt adhesives which is characterized by containing a urethane prepolymer having an isocyanate group in its end, a tackifying resin, and a compound having a structure represented by the foregoing formula (I).
In accordance with still another broad aspect of the present invention, there is provided a composition for moisture curing hot melt adhesives which is characterized by containing a urethane prepolymer having isocyanate group in its end, a tackifying resin, a thermoplastic polymer, and a compound having a structure represented by the foregoing formula (I).
The components of the composition for moisture curing hot melt adhesives according to the present invention are described in dletail below, Urethane prepolymer The urethane prepolymer used in the present invention is a urethane prepolymer having an isocyanate group in its end which is obtained by the addition reaction of polyols having a hydroxyl group or groups in its molecular end and polyisocyanates having an isocyanate group or groups in its molecular end.
As the above described polyols, conventionally known polyols generally used for the manufacture of polyurethane can be used. Examples of such polyols include polyester polyols, polyether polyols, polyalkylene polyols, and polycarbonate polyols.
More specifically, examples of the above described polyester polyols include polyester polyols obtained by the reaction of terephthalic acid, isophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, succinic acid, glutaric acid, adipic acid, picric acid, suberic acid, azelaic acid, sebacic acid, or dicarboxylic acids such as decamethylene dicarboxylic acid or dodecamethylene dicarboxylic acid and diols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol or cyclohexanediol; and poly-s-caprolactone-polyol obtained by ring-opening polymerization of e-caprolactam. E;Kamples of the above described polyether polyols include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
Examples of the above described polyalkylene polyol include polybutadiene polyol, polybutadiene polyol hydride, and polyisoprene polyol hydride. Examples of the above described polycarbonate polyols include polyhexamethylene~ carbonate polyol, and polycyclohexane dimethylene carbonate polyol. The above described types of polyols may be used alone or in combination.
Furthermore, examples of the above described polyisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, liquid denatured matter of diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, cyclohexane phenylene diisocyanate, and naphthalene-1, 5-dii.socyanate.
Compounds having a structure represented by formula (I) In the present invention, a compound having a structure represented by the formula (I) is added as a catalyst to the above described urethane prepolymer having one or more terminal isocyanate groups. This compound is a tertiary amine catalyst, as apparent from the above described formula (I). The use of thss catalyst makes it possible to obtain properties which are not obtained when the conventional catalyst is used. More specifically, both the moisture curing reactivity and the thermal stability are significantly enhanced by using the aforementioned catalyst.
Examples of the compound having the structure represented by the formula (I) include bis(2-(2,6-dimethyl-4-morpholino) ethyl) ~- (2-(4-morpholino) ethyl) amine, bis(2-(2,6-dimethyl-4-morpholino) ethyl) - (2-(2,6-diethyl-4-morpholino) ethyl) amine, tris(2-(4-morpholino) ethyl) amine, tris(2-(4-morpholino) propyl) amine, tris(2-(4-morpholino) butyl) amine, tris(2-(2,6-dimethyl-4-morpholino) ethyl) amine, tris(2-(2,6-diethyl-4-morpholino) ethyl) amine, tris(2-(2-methyl-4-morpholino) ethyl) amine or tris(2-(2-ethyl-4-morpholino) ethyl) amine.
The amount of addition of the compound having the structure represented by the formula (I) is in the range of 0.01 to 5 parts by weight and preferably, in the range of 0.1 to 2 parts by weight as the amount converted into the structure represented by the formula (I) per 100 parts by weight of a urethane prepolymer. The effect of accelerating the moisture curing reaction is not sufficiently obtained if the amount of addition is less than 0.01 parts by weight, while the thermal stability is lowered so that the adhesives may, in some cases, be gelled in the use if the amount of addition exceeds 5 parts by weight, which is not preferable.
In accordance with still another broad aspect of the present invention, there is provided a composition for moisture curing hot melt adhesives which is characterized by containing a urethane prepolymer having isocyanate group in its end, a tackifying resin, a thermoplastic polymer, and a compound having a structure represented by the foregoing formula (I).
The components of the composition for moisture curing hot melt adhesives according to the present invention are described in dletail below, Urethane prepolymer The urethane prepolymer used in the present invention is a urethane prepolymer having an isocyanate group in its end which is obtained by the addition reaction of polyols having a hydroxyl group or groups in its molecular end and polyisocyanates having an isocyanate group or groups in its molecular end.
As the above described polyols, conventionally known polyols generally used for the manufacture of polyurethane can be used. Examples of such polyols include polyester polyols, polyether polyols, polyalkylene polyols, and polycarbonate polyols.
More specifically, examples of the above described polyester polyols include polyester polyols obtained by the reaction of terephthalic acid, isophthalic acid, 1,5-naphthalic acid, 2,6-naphthalic acid, succinic acid, glutaric acid, adipic acid, picric acid, suberic acid, azelaic acid, sebacic acid, or dicarboxylic acids such as decamethylene dicarboxylic acid or dodecamethylene dicarboxylic acid and diols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol or cyclohexanediol; and poly-s-caprolactone-polyol obtained by ring-opening polymerization of e-caprolactam. E;Kamples of the above described polyether polyols include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
Examples of the above described polyalkylene polyol include polybutadiene polyol, polybutadiene polyol hydride, and polyisoprene polyol hydride. Examples of the above described polycarbonate polyols include polyhexamethylene~ carbonate polyol, and polycyclohexane dimethylene carbonate polyol. The above described types of polyols may be used alone or in combination.
Furthermore, examples of the above described polyisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, liquid denatured matter of diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, cyclohexane phenylene diisocyanate, and naphthalene-1, 5-dii.socyanate.
Compounds having a structure represented by formula (I) In the present invention, a compound having a structure represented by the formula (I) is added as a catalyst to the above described urethane prepolymer having one or more terminal isocyanate groups. This compound is a tertiary amine catalyst, as apparent from the above described formula (I). The use of thss catalyst makes it possible to obtain properties which are not obtained when the conventional catalyst is used. More specifically, both the moisture curing reactivity and the thermal stability are significantly enhanced by using the aforementioned catalyst.
Examples of the compound having the structure represented by the formula (I) include bis(2-(2,6-dimethyl-4-morpholino) ethyl) ~- (2-(4-morpholino) ethyl) amine, bis(2-(2,6-dimethyl-4-morpholino) ethyl) - (2-(2,6-diethyl-4-morpholino) ethyl) amine, tris(2-(4-morpholino) ethyl) amine, tris(2-(4-morpholino) propyl) amine, tris(2-(4-morpholino) butyl) amine, tris(2-(2,6-dimethyl-4-morpholino) ethyl) amine, tris(2-(2,6-diethyl-4-morpholino) ethyl) amine, tris(2-(2-methyl-4-morpholino) ethyl) amine or tris(2-(2-ethyl-4-morpholino) ethyl) amine.
The amount of addition of the compound having the structure represented by the formula (I) is in the range of 0.01 to 5 parts by weight and preferably, in the range of 0.1 to 2 parts by weight as the amount converted into the structure represented by the formula (I) per 100 parts by weight of a urethane prepolymer. The effect of accelerating the moisture curing reaction is not sufficiently obtained if the amount of addition is less than 0.01 parts by weight, while the thermal stability is lowered so that the adhesives may, in some cases, be gelled in the use if the amount of addition exceeds 5 parts by weight, which is not preferable.
The range of the amount of addition of the compound having the structure represented by the above described formula (I) varies depending on the type of polyol used for obtaining a urethane prepolymer. More specifically, it is preferable that the amount of addition of the compound having the structure reprE~sented by the above described formula (I) is in the range of 0.01 to 2 parts by weight per' 100 parts by weight of a urethane prepolymer which is obtained using, for example, polyester polyol, while being in the range of 0.05 to 5 parts by weight per 100 parts by weight of a urethane prepolymerwhich is obtained using, for example, polyalkylene polyol.
In either case, the amount of addition of the compound having the structure represented by the formula (I) is determined to a suitable range by experiments depending on the type of a urethane prepolymer used.
Tackifyin4 resin As described above, in accordance with another broad aspect of the present invention, a tackifying resin is contained in addition to the above described urethane prepolymer and compound having the structure represented by the formula (I).
The above described tackifying resin gives superior initial adhesive properties to the moisture curing type hot melt adhesives according to the present invention in cooperation with other adhesive components. Examples of the tackifying resin usable include rosin type resin, terpene type resin, aliphatic petroleum resin, cycloaliphatic petroleum resin or aromatic petroleum resin and preferably, ones whose ring and ball softening point is 80 to 150°C.
The types of tackifying resins may be used alone or in combination.
The amount of the above described tackifying resin is in the range of 5 to 200 parts by weight and preferably, in the range of 10 to 100 parts by weight per 100 parts by weight of a urethane prepolymer. The reason for this is 'that sufficient initial adhesive properties cannot be given to the composition for moisture curing type hot melt adhesives when the amount of the tackifying resin is less than 5 pacts by weight, while the adhesives become weak and particularly, are liable to be lacking in adhesive properties under a low temperature when it exceeds 200 parts by weight.
In either case, the amount of addition of the compound having the structure represented by the formula (I) is determined to a suitable range by experiments depending on the type of a urethane prepolymer used.
Tackifyin4 resin As described above, in accordance with another broad aspect of the present invention, a tackifying resin is contained in addition to the above described urethane prepolymer and compound having the structure represented by the formula (I).
The above described tackifying resin gives superior initial adhesive properties to the moisture curing type hot melt adhesives according to the present invention in cooperation with other adhesive components. Examples of the tackifying resin usable include rosin type resin, terpene type resin, aliphatic petroleum resin, cycloaliphatic petroleum resin or aromatic petroleum resin and preferably, ones whose ring and ball softening point is 80 to 150°C.
The types of tackifying resins may be used alone or in combination.
The amount of the above described tackifying resin is in the range of 5 to 200 parts by weight and preferably, in the range of 10 to 100 parts by weight per 100 parts by weight of a urethane prepolymer. The reason for this is 'that sufficient initial adhesive properties cannot be given to the composition for moisture curing type hot melt adhesives when the amount of the tackifying resin is less than 5 pacts by weight, while the adhesives become weak and particularly, are liable to be lacking in adhesive properties under a low temperature when it exceeds 200 parts by weight.
Thermoplastic polymer In accordance with still another aspect of the present invention, a thermoplastic polymer is contained in addition to the above described urethane prepolymer, a compound having the structure represented by the aforementioned formula (I), and tackifying resin.
The above described thermoplastic polymer gives superior initial adhesive properties and heat resistance to the composition for moisture curing hot melt adhesives according to the present invention in cooperation with other components.
Preferable examples of the above dE~scribed thermoplastic polymer include an A-(B-A)n block copolymer (where n is a number in the range of 1 to 50) or an A-B radial block copolymer when A is taken as a polystyrene block and B is taken as a rubber block. The above described A, that is, the polystyrene block contains a block unit containing polystyrene, poly a-methylstyrene and another similar aromatic monomer. In addition, B, that is, the rubber block may or may not be hydrogenated and contains isoprene, butadiene, another monomer capable of forming a rubbery polymer block, and a polymer manufactured from a repeated unit induced from their mixtures.
Specific examples of such an A-(B-A)n block copolymer or an A-B radial block copolymer include a styrene-butadiene-styrene copolymer (hereinafter abbreviated as SBS), a styrene-isoprene-styrene copolymer (SIS), and a styrene-ethylene-butylene-styrene copolymer (SEBS).
In addition, other preferable examples of the above described thermoplastic polymer include a vinyl polymer containing an ethylene-vinyl monomer copolymer whose melt index is approximately 0.1 to 1000 and which contains approximately 10 to 40 % by weight of a vinyl monomer or a vinyl polymer which contains 20 to 50 % by weight of a vinyl monomer, 40 to 77 by weight of ethylene, and 3 to 20 % by weight of carbon monoxide. Examples of this type of vinyl polymer include an ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVA).
In addition, the above described vinyl monomer includes an acrylate monomer or a vinyl ester monomer of a carboxylic acid compound. Examples of the above described vinyl polymer containing an acrylate monomer as a vinyl monomer include but are not limited to an ethylene-acrylic ester copolymer or an ethylene-methacrylic acid copolymer.
The above described thermoplastic polymer gives superior initial adhesive properties and heat resistance to the composition for moisture curing hot melt adhesives according to the present invention in cooperation with other components.
Preferable examples of the above dE~scribed thermoplastic polymer include an A-(B-A)n block copolymer (where n is a number in the range of 1 to 50) or an A-B radial block copolymer when A is taken as a polystyrene block and B is taken as a rubber block. The above described A, that is, the polystyrene block contains a block unit containing polystyrene, poly a-methylstyrene and another similar aromatic monomer. In addition, B, that is, the rubber block may or may not be hydrogenated and contains isoprene, butadiene, another monomer capable of forming a rubbery polymer block, and a polymer manufactured from a repeated unit induced from their mixtures.
Specific examples of such an A-(B-A)n block copolymer or an A-B radial block copolymer include a styrene-butadiene-styrene copolymer (hereinafter abbreviated as SBS), a styrene-isoprene-styrene copolymer (SIS), and a styrene-ethylene-butylene-styrene copolymer (SEBS).
In addition, other preferable examples of the above described thermoplastic polymer include a vinyl polymer containing an ethylene-vinyl monomer copolymer whose melt index is approximately 0.1 to 1000 and which contains approximately 10 to 40 % by weight of a vinyl monomer or a vinyl polymer which contains 20 to 50 % by weight of a vinyl monomer, 40 to 77 by weight of ethylene, and 3 to 20 % by weight of carbon monoxide. Examples of this type of vinyl polymer include an ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVA).
In addition, the above described vinyl monomer includes an acrylate monomer or a vinyl ester monomer of a carboxylic acid compound. Examples of the above described vinyl polymer containing an acrylate monomer as a vinyl monomer include but are not limited to an ethylene-acrylic ester copolymer or an ethylene-methacrylic acid copolymer.
Still other examples of the thermoplastic polymer used in the present invention include a polyolefin polymer such as atactic polypropylene (hereinafter abbreviated as APP) or an ethylene-a-olefin copolymer.
Meanwhile, the above described various types of thermoplastic polymers may be used alone or in combination.
The amount of the above described thermoplastic polymer is generally in the range of 10 to 100 parts by weight per 100 parts by weight of a urethane prepolymer.
The reason for this is that flexible and sufficient initial adhesive properties (adhesive strength immediately after adhesion which is not dependent on moisture curing) cannot be given to the composition for moisture curing hot melt adhesives according to the present invention when the amount of the thermoplastic polymer is less than 10 parts by weight per 100 parts by weight of a urethane prepolymer, while the adhesives cannot be applied unless the adhesives are heated to not less than 140°C, which significantly deteriorates the thermal stability of the adhesives because the melting viscosity of the adhesives is increased if the amount of the thermoplastic polymer exceeds 100 parts by weight per 100 parts by weight of a urethane prepolymer.
Other additives Other additives, for example, waxes such as paraffin wax or microcrystalline wax, inorganic and organic fillers, various oils or coloring agents may be suitable added within the range in which an object of the present invention is achieved to the composition for moisture curing hot melt adhesives.
According to the present invention. the compound having the structure represented by the formula (I) is added as a catalyst to the urethane prepolymer having an isocyanate group in its end. Accordingly, both the moisture curing reactivity and the thermal stability in the use are effectively enhanced. Consequently, if the composition for adhesives according to the present invention is used, sufficient heat resistance and adhesive strength are achieved without aging an adherend for an extensive period of time.
Meanwhile, the above described various types of thermoplastic polymers may be used alone or in combination.
The amount of the above described thermoplastic polymer is generally in the range of 10 to 100 parts by weight per 100 parts by weight of a urethane prepolymer.
The reason for this is that flexible and sufficient initial adhesive properties (adhesive strength immediately after adhesion which is not dependent on moisture curing) cannot be given to the composition for moisture curing hot melt adhesives according to the present invention when the amount of the thermoplastic polymer is less than 10 parts by weight per 100 parts by weight of a urethane prepolymer, while the adhesives cannot be applied unless the adhesives are heated to not less than 140°C, which significantly deteriorates the thermal stability of the adhesives because the melting viscosity of the adhesives is increased if the amount of the thermoplastic polymer exceeds 100 parts by weight per 100 parts by weight of a urethane prepolymer.
Other additives Other additives, for example, waxes such as paraffin wax or microcrystalline wax, inorganic and organic fillers, various oils or coloring agents may be suitable added within the range in which an object of the present invention is achieved to the composition for moisture curing hot melt adhesives.
According to the present invention. the compound having the structure represented by the formula (I) is added as a catalyst to the urethane prepolymer having an isocyanate group in its end. Accordingly, both the moisture curing reactivity and the thermal stability in the use are effectively enhanced. Consequently, if the composition for adhesives according to the present invention is used, sufficient heat resistance and adhesive strength are achieved without aging an adherend for an extensive period of time.
Accordingly, even if the composition for moisture curing hot melt adhesives according to the present invention is used for applications in which heat resistance is required, adhesion is possible in a short time, thereby malking it possible to significantly increase the productivity of a bonding operation.
In a drawing which illustrates an apparatus used in testing the invention, Fig. 1 is a perspective view of a pentite steel plate used in a heat-resistant creep test at 80°C for compositions of moisture curing hot melt adhesives in examples and comparative examples.
The present invention will be explained through non-restrictive examples and comparative examples of the present invention.
Example 1 200 parts by weight of polyalkylene polyol (POLYTAIL HA (trade mark) manufactured by Mitsubishi Chemical Industries, Ltd.;) and 52 parts by weight of diphenylmethane diisocyanate (MDI) are mixed with each other at a temperature of 100°C and are reacted with each other in an atmosphere of nitrogen for three hours, to obtain a urethane prepolymer (1). To 100 parts by weight of the urethane prepolymer (1) are added 30 parts by weight of saturated alicyclic hydrocarbon resin (ARKO~I P-125 (trade name) manufactured by Arakawa Chemical Industries, Ltd.) and a catalyst having a structure represented by either of the following variations of formula (I), (III) or (IV). These ingredients are then hot melt mixed with each other at a temperature of 150°C and then, the mixture obtained is vacuum deaerated, to obtain a composition for moisture curing hot melt adhesives.
Meanwhile the amount of addition of the catalyst represented by either formula (III) or (IV) is changed as shown in table 1 described hereafter, to obtain the four types of compositions for moisture curing hot melt adhesives in examples 1-a, 1-b, 1-c and 1-d.
C H s N -CH2~ N 0 ww (III) C H 3 ~ 3 CHs N CH2~ N 0 ...... (IV) ~ C H s IO Comparative Example 1 Four types of compositions for moisture curing type hot melt adhesives in comparative examples 1-a, 1-b, 1-c and 1-d are obtained as shown in table 1 described hereafter in the same manner as in example 1 except that dibutyl tin dilaurate (DBTDL), stannous octoate 15 (SnOct), triethylenediamine (TEDA), pentamethyl diethylenetriamine (PMDETA) are respectively used as catalysts.
Example 2 20 200 parts by weight of polytetramethylene adipate and 30 parts by weight of diphenylmethane diisocyanate (MDI) are mixed with e<~ch other at a temperature of 100°C
and are reacted with each other in an atmosphere of nitrogen for three hours, to obtain a urethane prepolymer (2).
To 100 parts by weight of the urethane prepolymer (2) are added 50 parts by weight of terpene-styrene resin (YS RESIN TO-125 (trade name) manufactured by Yasuhara Chemical 25 Co., Ltd.), 20 parts by weight of an a-olefin copolymer (BEST PLAST 708 (trade name) manufactured by Hules Co., Ltd.), and 0.4 parts by weight of the catalyst represented by the formula (III). These ingredients are hot mixed at a temperature of 150°C and then, the mixture obtained is vacuum deaerated to obtain a composition for moisture curing hot melt adhesives.
30 Comparative Example 2 A composition for moisture curing hot melt adhesives in a comparative example 2 is obtained in exactly the same manner as the example 2 except that the catalyst having the structure represented by the formula (III) is not added.
In a drawing which illustrates an apparatus used in testing the invention, Fig. 1 is a perspective view of a pentite steel plate used in a heat-resistant creep test at 80°C for compositions of moisture curing hot melt adhesives in examples and comparative examples.
The present invention will be explained through non-restrictive examples and comparative examples of the present invention.
Example 1 200 parts by weight of polyalkylene polyol (POLYTAIL HA (trade mark) manufactured by Mitsubishi Chemical Industries, Ltd.;) and 52 parts by weight of diphenylmethane diisocyanate (MDI) are mixed with each other at a temperature of 100°C and are reacted with each other in an atmosphere of nitrogen for three hours, to obtain a urethane prepolymer (1). To 100 parts by weight of the urethane prepolymer (1) are added 30 parts by weight of saturated alicyclic hydrocarbon resin (ARKO~I P-125 (trade name) manufactured by Arakawa Chemical Industries, Ltd.) and a catalyst having a structure represented by either of the following variations of formula (I), (III) or (IV). These ingredients are then hot melt mixed with each other at a temperature of 150°C and then, the mixture obtained is vacuum deaerated, to obtain a composition for moisture curing hot melt adhesives.
Meanwhile the amount of addition of the catalyst represented by either formula (III) or (IV) is changed as shown in table 1 described hereafter, to obtain the four types of compositions for moisture curing hot melt adhesives in examples 1-a, 1-b, 1-c and 1-d.
C H s N -CH2~ N 0 ww (III) C H 3 ~ 3 CHs N CH2~ N 0 ...... (IV) ~ C H s IO Comparative Example 1 Four types of compositions for moisture curing type hot melt adhesives in comparative examples 1-a, 1-b, 1-c and 1-d are obtained as shown in table 1 described hereafter in the same manner as in example 1 except that dibutyl tin dilaurate (DBTDL), stannous octoate 15 (SnOct), triethylenediamine (TEDA), pentamethyl diethylenetriamine (PMDETA) are respectively used as catalysts.
Example 2 20 200 parts by weight of polytetramethylene adipate and 30 parts by weight of diphenylmethane diisocyanate (MDI) are mixed with e<~ch other at a temperature of 100°C
and are reacted with each other in an atmosphere of nitrogen for three hours, to obtain a urethane prepolymer (2).
To 100 parts by weight of the urethane prepolymer (2) are added 50 parts by weight of terpene-styrene resin (YS RESIN TO-125 (trade name) manufactured by Yasuhara Chemical 25 Co., Ltd.), 20 parts by weight of an a-olefin copolymer (BEST PLAST 708 (trade name) manufactured by Hules Co., Ltd.), and 0.4 parts by weight of the catalyst represented by the formula (III). These ingredients are hot mixed at a temperature of 150°C and then, the mixture obtained is vacuum deaerated to obtain a composition for moisture curing hot melt adhesives.
30 Comparative Example 2 A composition for moisture curing hot melt adhesives in a comparative example 2 is obtained in exactly the same manner as the example 2 except that the catalyst having the structure represented by the formula (III) is not added.
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a ~ ~~j~~E~ ' a' : : a ~ E-l0 Evaluation of Examples 1 and 2 and Comparative Examples 1 and 2 A plate made of ABS resin having dimensions of 4 cm by 5 cm by 0.3 cm thick is spray-coated with each of the compositions for moisture curing hot melt adhesives in the examples 1-a to 1-d and the example 2 as well as the comparative examples 1-a to 1-d and the comparative example 2 obtained in the above described manner such that the amount of coating is 50 g/m2.
The above described plate made of ABS resin is then bonded to a pentite steel plate having a shape and dimensions shown in Fig. 1. A bond sample is cured in an atmosphere with a temperature of 20°C and 65 percent relative humidity, the bond surtace is kept horizontal with the pentite steel plate on the bottom, a suspension load of 100 g is applied to the pentite steel plate, and heat-resistant creep at a temperature of 80°C under the load of 100 g is measured.
The curing time period required until cohesive failure does not occur in the adhesives is an index of moisture curing characteristics.
Furthermore, each of the compositions for moisture curing hot melt adhesives outlined in the examples and the comparative examples, is placed in a sealed aluminum cartridge and heated at a temperature of 130°C for eight hours. The rate of viscosity increase (%) is measured and the same is used as an index of thermal stability.
The results of the moisture curing property and the thermal stability measured in the above described manner are shown in table 1. The meanings of the symbols used in table 1 are as shown in table 2.
Table 2 yloisture Curing Heat Stability Property Hour ) (%) p0 less than 4 less than 10 ( 0 4 to less than 12 10 to less than 50 0 12 to less than 24 50 to less than 100 24 or more 100 As obvious from the table 1, the compositions for moisture curing hot melt adhesives in the examples 1-a to 1-d and the example 2 exhibit sufficiently superior moisture curing property and thermal stability. By contrast, the compositions for moisture curing hot melt adhesives in the comparative example 1-a and the comparative example 2 are significantly inferior in moisture curing property, while the composition for moisture curing hot melt adhesives in the comparative example 1-b is significantly inferior in thermal stability.
Meanwhile, in each of the compositions for moisture curing type hot melt adhesives in the comparative examples 1-c and 1-d, the catalyst evaporates at the time of mixing adhesives, so that the above described respective evaluations cannot be carried out.
Example 3 50 parts by weight of saturated alicyclic hydrocarbon resin (ARKON P-125 (trade name) manufactured by Arakawa Chemical Industries, Ltd.) and 30 parts by weight of an a-olefin copolymer (BEST PLAST 708 (trade name) manufactured by Hules Co., Ltd.) are melt mixed with each other at a temperature of 150°C. To the mixture obtained, 100 parts by weight of a urethane prepolymer (1) obtained in the example 1 and varying amounts of the catalyst having the structure represented by the formula (III) shown in the example 1 are further added and the ingredients are agitated for thirty minutes while being vacuum deaerated, thereby to obtain a composition for moisture curing hot melt adhesives.
The amount of addition of the catalyst represented by the formula (III) is changed as shown in the following table 3, thereby to obtain three different compositions for moisture curing hot melt adhesives in examples 3-a, 3-b and 3-c.
Com~aarative Example 3 Four types of compositions for moisture curing hot melt adhesives in comparative examples 3-a, 3-b, 3-c and 3-d are obtained as shown in the following table 4 in the same manner as the example 3 except that dibutyltin dilaurate (DBTDL), stannous octoate (SnOct), triethylenediamine (TEDA), pentamethyl diethylenetriamine (PMDETA) are respectively used as catalysts.
Example 4 60 parts by weight of hydrogenated terpene resin (CLEARON P-115 (trade mark) manufactured by Yasuhara Chemical Co., Ltd.) and 60 parts by weight of ethylene-ethyl acrylate resin (EEA-704 (trade name) manufactured by Dupont-Mitsui Polychemicals Co., Ltd.) are melt mixed with each other at a temperature of 150°C. To the mixture obtained, 100 parts by weight of a urethane prepolymer (1 ) obtained in the example 1 and 0.5 parts by weight of the catalyst having the structure represented by the foregoing formula (III) are further added and the ingredients are agitated for thirty minutes while being vacuum deaerated, thereby to obtain a composition for moisture curing hot melt adhesives.
Example 5 50 parts by weight of styrene system hydrocarbon resin (FTR-6100 (trade name) manufactured by Mitsui Petrochemical Industries, Ltd.) and 20 parts by weight of an etyrene-butyl acrylate-carbon monoxide copolymer (EP-4043 (trade name) manufactured by Dupont Co., Ltd.) are melt mixed with each other at a temperature of 150°C. To the mixture obtained, 100 parts by weight of the urethane prepolymer (1 ) obtained in the example 1 and 0.4 parts by weight of the catalyst having the structure represented by the formula (IV) shown in the example 1 are further added and the ingredients are agitated for thirty minutes while being vacuum deaerated, thereby to obtain a composition for moisture curing type hot melt adhesives.
Example 6 100 parts by weight of saturated alicyclic hydrocarbon resin (ARKON P-100 (trade name) manufactured by Arakawa Chemical Industries, Ltd.) and 30 parts by weight of SEES as the thermoplastic elastomer (CRATON ~~-1726 (trade mark) manufactured by Shell Kagaku K.K.) are thoroughly mixed with each other at a temperature of 140°C using a double arm mixer.
To the mixture obtained, 100 parts Iby weight of the urethane prepolymer (1) obtained in the example 1 and 0.3 parts by weight of the catalyst having the structure represented by the foregoing formula (IV) are further added and the ingredients are agitated for thirty minutes while being vacuum deaerated, thereby to obtain a composition for moisture curing type hot melt adhesives.
Example 7 parts by weight of disproportionaired rosin ester resin (SUPER ESTER A-100 (trade name) manufactured by Arakawa Chemical Industries, Ltd.) are hot melted, and 100 parts by weight S of the urethane prepolymer (2) obtained in the example 2 and 0.3 parts by weight of the catalyst represented by the foregoing formula (III) are further melt mixed with the melted rosin ester resin and are vacuum deaerated at a temperature of 130°C, to obtain a composition for moisture curing type hot melt adhesives.
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a ~ ~~j~~E~ ' a' : : a ~ E-l0 Evaluation of Examples 1 and 2 and Comparative Examples 1 and 2 A plate made of ABS resin having dimensions of 4 cm by 5 cm by 0.3 cm thick is spray-coated with each of the compositions for moisture curing hot melt adhesives in the examples 1-a to 1-d and the example 2 as well as the comparative examples 1-a to 1-d and the comparative example 2 obtained in the above described manner such that the amount of coating is 50 g/m2.
The above described plate made of ABS resin is then bonded to a pentite steel plate having a shape and dimensions shown in Fig. 1. A bond sample is cured in an atmosphere with a temperature of 20°C and 65 percent relative humidity, the bond surtace is kept horizontal with the pentite steel plate on the bottom, a suspension load of 100 g is applied to the pentite steel plate, and heat-resistant creep at a temperature of 80°C under the load of 100 g is measured.
The curing time period required until cohesive failure does not occur in the adhesives is an index of moisture curing characteristics.
Furthermore, each of the compositions for moisture curing hot melt adhesives outlined in the examples and the comparative examples, is placed in a sealed aluminum cartridge and heated at a temperature of 130°C for eight hours. The rate of viscosity increase (%) is measured and the same is used as an index of thermal stability.
The results of the moisture curing property and the thermal stability measured in the above described manner are shown in table 1. The meanings of the symbols used in table 1 are as shown in table 2.
Table 2 yloisture Curing Heat Stability Property Hour ) (%) p0 less than 4 less than 10 ( 0 4 to less than 12 10 to less than 50 0 12 to less than 24 50 to less than 100 24 or more 100 As obvious from the table 1, the compositions for moisture curing hot melt adhesives in the examples 1-a to 1-d and the example 2 exhibit sufficiently superior moisture curing property and thermal stability. By contrast, the compositions for moisture curing hot melt adhesives in the comparative example 1-a and the comparative example 2 are significantly inferior in moisture curing property, while the composition for moisture curing hot melt adhesives in the comparative example 1-b is significantly inferior in thermal stability.
Meanwhile, in each of the compositions for moisture curing type hot melt adhesives in the comparative examples 1-c and 1-d, the catalyst evaporates at the time of mixing adhesives, so that the above described respective evaluations cannot be carried out.
Example 3 50 parts by weight of saturated alicyclic hydrocarbon resin (ARKON P-125 (trade name) manufactured by Arakawa Chemical Industries, Ltd.) and 30 parts by weight of an a-olefin copolymer (BEST PLAST 708 (trade name) manufactured by Hules Co., Ltd.) are melt mixed with each other at a temperature of 150°C. To the mixture obtained, 100 parts by weight of a urethane prepolymer (1) obtained in the example 1 and varying amounts of the catalyst having the structure represented by the formula (III) shown in the example 1 are further added and the ingredients are agitated for thirty minutes while being vacuum deaerated, thereby to obtain a composition for moisture curing hot melt adhesives.
The amount of addition of the catalyst represented by the formula (III) is changed as shown in the following table 3, thereby to obtain three different compositions for moisture curing hot melt adhesives in examples 3-a, 3-b and 3-c.
Com~aarative Example 3 Four types of compositions for moisture curing hot melt adhesives in comparative examples 3-a, 3-b, 3-c and 3-d are obtained as shown in the following table 4 in the same manner as the example 3 except that dibutyltin dilaurate (DBTDL), stannous octoate (SnOct), triethylenediamine (TEDA), pentamethyl diethylenetriamine (PMDETA) are respectively used as catalysts.
Example 4 60 parts by weight of hydrogenated terpene resin (CLEARON P-115 (trade mark) manufactured by Yasuhara Chemical Co., Ltd.) and 60 parts by weight of ethylene-ethyl acrylate resin (EEA-704 (trade name) manufactured by Dupont-Mitsui Polychemicals Co., Ltd.) are melt mixed with each other at a temperature of 150°C. To the mixture obtained, 100 parts by weight of a urethane prepolymer (1 ) obtained in the example 1 and 0.5 parts by weight of the catalyst having the structure represented by the foregoing formula (III) are further added and the ingredients are agitated for thirty minutes while being vacuum deaerated, thereby to obtain a composition for moisture curing hot melt adhesives.
Example 5 50 parts by weight of styrene system hydrocarbon resin (FTR-6100 (trade name) manufactured by Mitsui Petrochemical Industries, Ltd.) and 20 parts by weight of an etyrene-butyl acrylate-carbon monoxide copolymer (EP-4043 (trade name) manufactured by Dupont Co., Ltd.) are melt mixed with each other at a temperature of 150°C. To the mixture obtained, 100 parts by weight of the urethane prepolymer (1 ) obtained in the example 1 and 0.4 parts by weight of the catalyst having the structure represented by the formula (IV) shown in the example 1 are further added and the ingredients are agitated for thirty minutes while being vacuum deaerated, thereby to obtain a composition for moisture curing type hot melt adhesives.
Example 6 100 parts by weight of saturated alicyclic hydrocarbon resin (ARKON P-100 (trade name) manufactured by Arakawa Chemical Industries, Ltd.) and 30 parts by weight of SEES as the thermoplastic elastomer (CRATON ~~-1726 (trade mark) manufactured by Shell Kagaku K.K.) are thoroughly mixed with each other at a temperature of 140°C using a double arm mixer.
To the mixture obtained, 100 parts Iby weight of the urethane prepolymer (1) obtained in the example 1 and 0.3 parts by weight of the catalyst having the structure represented by the foregoing formula (IV) are further added and the ingredients are agitated for thirty minutes while being vacuum deaerated, thereby to obtain a composition for moisture curing type hot melt adhesives.
Example 7 parts by weight of disproportionaired rosin ester resin (SUPER ESTER A-100 (trade name) manufactured by Arakawa Chemical Industries, Ltd.) are hot melted, and 100 parts by weight S of the urethane prepolymer (2) obtained in the example 2 and 0.3 parts by weight of the catalyst represented by the foregoing formula (III) are further melt mixed with the melted rosin ester resin and are vacuum deaerated at a temperature of 130°C, to obtain a composition for moisture curing type hot melt adhesives.
10 Comparative Example 4 A composition for moisture curing hot melt adhesives is obtained in the same manner as in example 7 except that no catalyst is added.
1 S Example 8 200 parts by weight of polytetrametylene glycol and 35 parts by weight of diphenylmethane diisocyanate (MDI) are mixed with each other at a temperature of 80°C
and are reacted with each other under an atmosphere of nitrogen for four hours, to obtain a urethane prepolymer (3).
80 parts by weight of disproportionated rosin ester resin (SUPER ESTER A-100 (trade name) manufactured by Arakawa Chemical Industries, Ltd.) is hot melted, and 100 parts by weight of urethane prepolymer (3) and 0.4 parts by weight of the catalyst represented by the foregoing 2S formula (IV) are melt mixed with the rosin ester resin and are vacuum deaerated at a temperature of 130°C, to obtain a composition for moisture curing hot melt adhesives.
Comparative Example 5 A composition for moisture curing type hot melt adhesives is obtained in the same manner as outlined in example 8 except that the amount of catalyst is 6.0 parts by weight.
Evaluation of Examples 3 to 8 and comparative Examples 3 to 5 The evaluations of moisture curing property and thermal stability are carried out in the same manner as the examples 1 and 2 and the comparative examples 1 and 2 with respect to each S of the composition for moisture curing hot melt adhesives in the examples 3 to 8 and the comparative examples 3 to 5 obtained in the above described manner. The results of the evaluations are shown in tables 3 and 4. The symbols of evaluation in tables 3 and 4 are described in table 2.
As apparent from tables 3 and 4, the compositions for moisture curing hot melt adhesives in the examples 3 to 8 exhibit sufficiently superior moisture curing property and thermal stability.
By contrast, the compositions for moisture curing type hot melt adhesives in the comparative example 3-a and the comparative example 4 are significantly inferior in moisture curing property, while the compositions for moisture curing hot melt adhesives in the comparative example 3-b and the comparative example 5 are significantly inferior in thermal stability.
Meanwhile, in the compositions for moisture curing hot melt adhesives in the comparative examples 3-c and 3-d, the catalyst evaporates at the time of mixing adhesives, sa that the above described respective evaluatiions cannot be carried out.
Tab 1 a Example 3-a 3-b 3-c 4 5 6 7 ( 8 Urethane Prepolymer ( 1 > loo loo loo loo loo loo .. ..
(2) loo (3> ~ loo Tackifying Resin SUPER ESTER A - 100 to so Thermoplastic Polymer ......................................~........ ........ ........ ........
...__... ........ ........ ........
BESTPLAST 708 ( 30 30 30 i ......................................k........ ........ ........ ........
........ ........ ........ ........
EEA-704 i 60 ......................................;........ ........ ........ ........
........ ........ ........ ........
Catalyst Catalyst of Formula(III) 0.1 ~ 0.5 2.0 0.5 0.3 Catalyst of FormulaCIV) 0.4 0.3 0.4 DBTDL
SnOct TEDA
P~11DETA
Moisture Curing Property p Oo O O O O O O
.Thermal Stability............. ....~.. .Ø_ ..Q.. Ø. .Ø. .Ø. Ø.
Table 4 Comparative Example 3-aI 3-b 3-c 3-d 4 5 I
Urethane Prepolymer ( 1 ) 100 i 1 100 (2) 100 (3) 100 Tackifying Resin .......................................a ........................................
........
CLEARON P-115 j SUPER ESTER A - 100 10 l0 Thermoplastic Polymer Catalyst Catalyst of Formula(III) Catalyst of Formula((V) 6.0 DBTDL 0.
SnOc t 0.
TEDA 0.
P61DETA 0.
6ioisture Curing X O -PropE:rty Thermal Stability D X - - ~ x
1 S Example 8 200 parts by weight of polytetrametylene glycol and 35 parts by weight of diphenylmethane diisocyanate (MDI) are mixed with each other at a temperature of 80°C
and are reacted with each other under an atmosphere of nitrogen for four hours, to obtain a urethane prepolymer (3).
80 parts by weight of disproportionated rosin ester resin (SUPER ESTER A-100 (trade name) manufactured by Arakawa Chemical Industries, Ltd.) is hot melted, and 100 parts by weight of urethane prepolymer (3) and 0.4 parts by weight of the catalyst represented by the foregoing 2S formula (IV) are melt mixed with the rosin ester resin and are vacuum deaerated at a temperature of 130°C, to obtain a composition for moisture curing hot melt adhesives.
Comparative Example 5 A composition for moisture curing type hot melt adhesives is obtained in the same manner as outlined in example 8 except that the amount of catalyst is 6.0 parts by weight.
Evaluation of Examples 3 to 8 and comparative Examples 3 to 5 The evaluations of moisture curing property and thermal stability are carried out in the same manner as the examples 1 and 2 and the comparative examples 1 and 2 with respect to each S of the composition for moisture curing hot melt adhesives in the examples 3 to 8 and the comparative examples 3 to 5 obtained in the above described manner. The results of the evaluations are shown in tables 3 and 4. The symbols of evaluation in tables 3 and 4 are described in table 2.
As apparent from tables 3 and 4, the compositions for moisture curing hot melt adhesives in the examples 3 to 8 exhibit sufficiently superior moisture curing property and thermal stability.
By contrast, the compositions for moisture curing type hot melt adhesives in the comparative example 3-a and the comparative example 4 are significantly inferior in moisture curing property, while the compositions for moisture curing hot melt adhesives in the comparative example 3-b and the comparative example 5 are significantly inferior in thermal stability.
Meanwhile, in the compositions for moisture curing hot melt adhesives in the comparative examples 3-c and 3-d, the catalyst evaporates at the time of mixing adhesives, sa that the above described respective evaluatiions cannot be carried out.
Tab 1 a Example 3-a 3-b 3-c 4 5 6 7 ( 8 Urethane Prepolymer ( 1 > loo loo loo loo loo loo .. ..
(2) loo (3> ~ loo Tackifying Resin SUPER ESTER A - 100 to so Thermoplastic Polymer ......................................~........ ........ ........ ........
...__... ........ ........ ........
BESTPLAST 708 ( 30 30 30 i ......................................k........ ........ ........ ........
........ ........ ........ ........
EEA-704 i 60 ......................................;........ ........ ........ ........
........ ........ ........ ........
Catalyst Catalyst of Formula(III) 0.1 ~ 0.5 2.0 0.5 0.3 Catalyst of FormulaCIV) 0.4 0.3 0.4 DBTDL
SnOct TEDA
P~11DETA
Moisture Curing Property p Oo O O O O O O
.Thermal Stability............. ....~.. .Ø_ ..Q.. Ø. .Ø. .Ø. Ø.
Table 4 Comparative Example 3-aI 3-b 3-c 3-d 4 5 I
Urethane Prepolymer ( 1 ) 100 i 1 100 (2) 100 (3) 100 Tackifying Resin .......................................a ........................................
........
CLEARON P-115 j SUPER ESTER A - 100 10 l0 Thermoplastic Polymer Catalyst Catalyst of Formula(III) Catalyst of Formula((V) 6.0 DBTDL 0.
SnOc t 0.
TEDA 0.
P61DETA 0.
6ioisture Curing X O -PropE:rty Thermal Stability D X - - ~ x
Claims (17)
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A composition for moisture curing hot melt adhesives, comprising:
a urethane prepolymer having one or more terminal isocyanate groups; and a compound having a structure represented by the following formula:
in an amount ranging from 0.01 to 5 parts by weight, per 100 parts by weight of the urethane prepolymer, where X, Y and Z in the formula (I) are alkyl groups or groups represented by the following formula (II), and at least one of X, Y and Z is a group represented by the following formula (II):
n in the formula (II) is an integer from 1 through 10, and R1 and R2 are hydrogen or alkyl groups.
a urethane prepolymer having one or more terminal isocyanate groups; and a compound having a structure represented by the following formula:
in an amount ranging from 0.01 to 5 parts by weight, per 100 parts by weight of the urethane prepolymer, where X, Y and Z in the formula (I) are alkyl groups or groups represented by the following formula (II), and at least one of X, Y and Z is a group represented by the following formula (II):
n in the formula (II) is an integer from 1 through 10, and R1 and R2 are hydrogen or alkyl groups.
2. The composition for moisture curing hot melt adhesives according to claim 1, wherein the urethane prepolymer having one or more terminal isocyanate groups is obtained by the addition reaction of polyol having one or more terminal hydroxyl groups and polyisocyanate having one or more terminal isocyanate groups.
3. The composition for moisture curing hot melt adhesives according to claim 2, wherein the polyol having one or more terminal hydroxyl groups is at least one type selected from the group consisting of polyester polyol, polyether polyol, polyalkylene polyol and polycarbonate polyol.
4. The composition for moisture curing hot melt adhesives according to claim 3, wherein the polyol is polyalkylene polyol, and the polyalkylene polyol contains polybutadiene polyol.
5. The composition for moisture curing hot melt adhesives according to claim 4, wherein the polybutadiene polyol contains polybutadiene polyol hydride.
6. The composition for moisture curing hot melt adhesives according to any one of claims 1 to 5, being characterized in that the amount of said compound represented by the formula (I) is in the range of 0.1 to 2 parts by weight, per 100 parts by weight of the urethane prepolymer.
7. A composition for moisture curing hot melt adhesives, comprising:
a urethane prepolymer having one or more terminal isocyanate groups;
a tackifying resin in an amount ranging from 5 to 200 parts by weight, per 100 parts by weight of the urethane prepolymer; and a compound having a structure represented by the following formula (I):
in an amount ranging from 0.01 to 5 parts by weight, per 100 parts by weight of the urethane prepolymer where X, Y and Z in the formula (I) are alkyl groups or groups represented by the following formula (II), and at least one of X, Y and Z is a group represented by the following formula (II):
n in the formula (II) is an integer from 1 through 10, and R1 and R2 are hydrogen or alkyl groups.
a urethane prepolymer having one or more terminal isocyanate groups;
a tackifying resin in an amount ranging from 5 to 200 parts by weight, per 100 parts by weight of the urethane prepolymer; and a compound having a structure represented by the following formula (I):
in an amount ranging from 0.01 to 5 parts by weight, per 100 parts by weight of the urethane prepolymer where X, Y and Z in the formula (I) are alkyl groups or groups represented by the following formula (II), and at least one of X, Y and Z is a group represented by the following formula (II):
n in the formula (II) is an integer from 1 through 10, and R1 and R2 are hydrogen or alkyl groups.
8. The composition for moisture curing hot melt adhesives according to claim 7, wherein the tackifying resin is selected from the group consisting of rosin type resin, terpene type resin, aliphatic petroleum resin, alicyclic petroleum resin and aromatic petroleum resin or mixtures thereof.
9. The composition for moisture curing hot melt adhesives according to claim 8, wherein the amount of the tackifying resin is in the range of 10 to 100 parts by weight, per 100 parts by weight of the urethane prepolymer.
10. The composition for moisture curing hot melt adhesives according to claim 8, wherein the ring and ball softening point of the tackifying resin is 80 to 150°C.
11. The composition for moisture curing hot melt adhesives according to any one of claims 7 to 10, characterized in that the amount of the compound represented by the formula (I) is in the range of 0.1 to 2 parts by weight, per 100 parts by weight of the urethane prepolymer.
12. A composition for moisture curing hot melt adhesives, comprising:
a urethane prepolymer having one or more terminal isocyanate groups;
a tackifying resin in an amount ranging from 5 to 200 parts by weight, per 100 parts by weight of the urethane prepolymer;
a thermoplastic polymer in an amount ranging from 10 to 100 parts by weight, per 100 parts by weight of the urethane prepolymer; and a compound having a structure represented by the following formula (I):
in an amount ranging from 0.01 to 5 parts by weight, per 100 parts by weight of the urethane prepolymer where X, Y and Z in the formula (I) are alkyl groups or groups represented by the following formula (II), and at least one of X, Y and Z is a group represented by the following formula (II):
n in the formula (II) is an integer from 1 through 10, and R1 and R2 are hydrogen or alkyl groups.
a urethane prepolymer having one or more terminal isocyanate groups;
a tackifying resin in an amount ranging from 5 to 200 parts by weight, per 100 parts by weight of the urethane prepolymer;
a thermoplastic polymer in an amount ranging from 10 to 100 parts by weight, per 100 parts by weight of the urethane prepolymer; and a compound having a structure represented by the following formula (I):
in an amount ranging from 0.01 to 5 parts by weight, per 100 parts by weight of the urethane prepolymer where X, Y and Z in the formula (I) are alkyl groups or groups represented by the following formula (II), and at least one of X, Y and Z is a group represented by the following formula (II):
n in the formula (II) is an integer from 1 through 10, and R1 and R2 are hydrogen or alkyl groups.
13. The composition for moisture curing hot melt adhesives according to claim 12, wherein the thermoplastic polymer is a type of polymer selected from the group consisting of an A-(B-A)n block copolymer and an A-B radial block copolymer, where A is a polystyrene block, B is a rubber block, and n is from 1 through 50.
14. The composition for moisture curing hot melt adhesives according to claim 12, wherein the thermoplastic polymer is a vinyl polymer containing ethylene-vinyl monomer copolymer whose melt index is approximately 0.1 to 1000 and which contains approximately 10 to 40 percent by weight of a vinyl monomer.
15. The composition for moisture curing hot melt adhesives according to claim 12, wherein the thermoplastic polymer is ethylene copolymer containing 20 to 50 % by weight of vinyl monomer, 50 to 75 % by weight of ethylene, and 3 to 20 % by weight of carbon monoxide.
16. The composition for moisture curing hot melt adhesives according to claim 12, wherein the thermoplastic polymer is polyolefin polymer.
17. The composition for moisture curing hot melt adhesives according to any one of claims 12 to 16, being characterized in that the amount of the compound represented by the formula (I) is in the range of 0.1 to 2 parts by weight, per 100 parts by weight of the urethane prepolymer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3075161A JPH04309515A (en) | 1991-04-08 | 1991-04-08 | Moisture-curing hot melt adhesive composition |
| JP75161/1991 | 1991-04-08 | ||
| PCT/JP1992/000428 WO1992017556A1 (en) | 1991-04-08 | 1992-04-06 | Moisture-curable hot-melt adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2080459A1 CA2080459A1 (en) | 1992-10-09 |
| CA2080459C true CA2080459C (en) | 2002-09-17 |
Family
ID=13568206
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002080459A Expired - Fee Related CA2080459C (en) | 1991-04-08 | 1992-04-06 | Compositions for moisture curing hot melt adhesives |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0532765B1 (en) |
| JP (1) | JPH04309515A (en) |
| CA (1) | CA2080459C (en) |
| DE (1) | DE69225937T2 (en) |
| WO (1) | WO1992017556A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU667448B2 (en) * | 1994-02-22 | 1996-03-21 | National Starch And Chemical Investment Holding Corporation | Catalyst for reactive hot melt adhesives |
| US5616625A (en) * | 1995-02-17 | 1997-04-01 | National Starch And Chemical Investment Holding Corporation | Reactive hot melt foam |
| DE69706771T2 (en) * | 1996-06-19 | 2002-07-04 | H.B. Fuller Licensing & Financing, Inc. | Thermoplastic polyurethanes for bookbinding |
| WO1998058005A1 (en) * | 1997-06-18 | 1998-12-23 | H.B. Fuller Licensing & Financing, Inc. | Catalyzed reactive hot melts |
| JP4734686B2 (en) * | 1999-11-18 | 2011-07-27 | 荒川化学工業株式会社 | Tackifier for polyurethane adhesive, binder for polyurethane adhesive, and polyurethane adhesive composition |
| JP2011116817A (en) * | 2009-12-01 | 2011-06-16 | Henkel Japan Ltd | Moisture-curable hot melt adhesive |
| JP5445223B2 (en) * | 2010-03-02 | 2014-03-19 | 東洋アドレ株式会社 | Moisture curable adhesive composition |
| JP5510141B2 (en) * | 2010-07-16 | 2014-06-04 | 東洋アドレ株式会社 | Method for producing urethane-based moisture-curable adhesive composition |
| JP7298070B2 (en) * | 2019-12-17 | 2023-06-27 | 東洋インキＳｃホールディングス株式会社 | Moisture-curable hot-melt adhesive, book using said adhesive, and method for manufacturing book |
| JP6916404B1 (en) * | 2021-03-05 | 2021-08-11 | 第一工業製薬株式会社 | Two-component curable polyurethane resin composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA979600A (en) * | 1971-01-25 | 1975-12-09 | Rocco L. Mascioli | Catalyzing urethane foam polymerization with 4-(2-dimethylaminoethyl) morpholine |
| DE3046905A1 (en) * | 1980-12-12 | 1982-07-15 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING GGF. FOAMED POLYURETHANE |
| JPS5813618A (en) * | 1981-07-17 | 1983-01-26 | Yoshitomi Pharmaceut Ind Ltd | Preparation of polyurethane polymer |
| JP2665371B2 (en) * | 1989-03-16 | 1997-10-22 | サンアプロ株式会社 | Amine compound, production method and catalyst for urethanation reaction |
| JPH03135970A (en) * | 1989-10-23 | 1991-06-10 | San Apuro Kk | Amine compound, production thereof and catalyst for urethanating |
| JPH03179017A (en) * | 1989-12-07 | 1991-08-05 | Mitsui Toatsu Chem Inc | Manufacturing method of semi-rigid polyurethane foam |
-
1991
- 1991-04-08 JP JP3075161A patent/JPH04309515A/en active Pending
-
1992
- 1992-04-06 CA CA002080459A patent/CA2080459C/en not_active Expired - Fee Related
- 1992-04-06 WO PCT/JP1992/000428 patent/WO1992017556A1/en active IP Right Grant
- 1992-04-06 DE DE69225937T patent/DE69225937T2/en not_active Expired - Fee Related
- 1992-04-06 EP EP92907995A patent/EP0532765B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE69225937T2 (en) | 1999-02-25 |
| EP0532765B1 (en) | 1998-06-17 |
| EP0532765A4 (en) | 1993-09-15 |
| DE69225937D1 (en) | 1998-07-23 |
| EP0532765A1 (en) | 1993-03-24 |
| CA2080459A1 (en) | 1992-10-09 |
| WO1992017556A1 (en) | 1992-10-15 |
| JPH04309515A (en) | 1992-11-02 |
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